Dispersant material for mitigating crude oil fouling of process equipment and method for using same

ABSTRACT

An improved dispersant material for mitigating crude oil fouling comprises a reaction product of a polyamine and a polyisobutylene succinyl anhydride made with a polyisobutylene having a vinylidene double bond content of at least 50%. The reaction product has an active nitrogen atom content of at least about 2% by weight. The reaction product is prepared by thermally reacting the polyisobutylene with maleic anhydride to produce said polyisobutylene succinyl anhydride and thereafter reacting the polyisobutylene succinyl anhydride with a polyamine having 5 to 7 active nitrogen atoms.

CROSS REFERENCE TO RELATED APPLICATIONS

None

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to dispersant materials useful formitigating and/or inhibiting fouling of equipment used for handlingand/or treating liquid hydrocarbons such as crude oil and the like, andparticularly to improved antifoulant materials based on a reactionproduct of a hydrocarbon long chain such as polyisobutylene (PIB), abridging agent such as maleic anhydride and a substance having a polargroup such as a polyamine (PAM). Such products are sometimes referred togenerically as PIBSA-PAMs. The invention also relates to methodologyuseful for mitigating the fouling tendencies of crude oils and the likewhich includes the addition of an improved fouling mitigating and/orinhibiting dispersant material thereto. Furthermore, the inventionrelates to improved crude oil compositions wherein fouling tendencieshave been mitigated by the presence therein of improved foulingmitigating and/or inhibiting dispersant materials.

2. Background of the Invention

Crude oil is complex mixture composed of many components which varygreatly in their chemical and physical properties. The basic componentsof crude oils include saturated hydrocarbons, naphthenes, resins,aromatics and macromolecular asphaltenes. Crude oils are classified asnaphthinic, aromatic or paraffinic, depending upon the relativeconcentrations of these ingredients. Asphaltenes are present in mostcrude oils; however, the concentration thereof may vary from about 0.1wt % to as much as 12 wt %, depending on the origin of the crude.Asphaltenes are highly aromatic conglomerates with very high molecularweights, and the same may generally be characterized as alkyl aromaticsconsisting of polycondensed aromatics of six or more rings. Asphaltenesare at least partially soluble in aromatics. However, the same aregenerally insoluble in saturated hydrocarbons, and, as a result,asphaltenes usually exist in crude oils in the form of a suspension thatis stabilized by the resin fraction which acts as a natural dispersant.

As is well known in the petrochemical industry, in order to beneficiatecrude oils and produce valuable commercial products therefrom, it isgenerally necessary to subject the crude oil materials to distillationand/or cracking operations, or the like, wherein the crude oil materialsare subjected to high temperatures. However, when crude oils, andparticularly those that are deficient in aromatics and/or resins, aresubjected to the high temperatures needed for processing, theasphaltenes and other undesirable carbonaceous materials becomeincompatible with the liquid phase and tend to flocculate and/orprecipitate so as to deposit and accumulate on hot metal internalsurfaces of processing equipment. This accumulation of undesirablecarbonaceous materials on the internal surfaces of process equipment isoften referred to as “fouling.” And fouling often causes seriousoperational problems such as reduced heat transfer efficiency andincreased pressure drop characteristics. In fact, in some cases foulingis of sufficient magnitude to totally block flow through the equipment.Moreover, fouling often may be the cause of increased metal corrosion.

Needless to say, the fouling of process equipment such as heatexchangers and/or furnace tubes, for example, is a costly problem inrefineries and petrochemical plants and the like, since the fouledequipment must be dismantled, cleaned and reassembled. Such cleaningoperations are not only tedious and costly, but result in a large amountof “downtime” during which the units are not functioning.

It is known that certain dispersants of specific chemical structure canmitigate and/or inhibit fouling of process equipment by crude oils andthe like. Such dispersants generally function to disperse and suspend inthe liquid phase undesirable carbonaceous materials such as asphaltenemacromolecules that form during heating of the crude oil. Thus, thesedispersants inhibit and/or prevent the accumulation of undesirablecarbonaceous materials on the internal surfaces of the equipment.Generally speaking, these known dispersants have polar atoms which mayfunction to chelate with the undesirable carbonaceous materials tothereby assist in the dispersion of the same in the liquid phase.Accordingly, the undesirable carbonaceous materials are kept insuspension and not allowed to flocculate out for accumulation on theinternal surfaces of the process equipment.

Known dispersants for mitigating fouling during processing of crude oilsand the like often include a long chain hydrocarbon portion to providesolubility of the dispersant in oil and a polar functionality groupproviding an active site capable of chelation with undesirablecarbonaceous materials such as asphaltene macromolecules, whereby thelatter are kept in a suspended, dispersed condition in the crude oil.These polar functionality groups often include oxygen and/or nitrogenatoms which facilitate efficient chelation and the resultant dispersionof the asphaltene. Known dispersants may also desirably have lowviscosity and good thermal stability to appropriately withstand thehostile environment in which the same are utilized.

Polyisobutylene succinyl anhydride-polyamine compounds, which are oftenreferred to as PIBSA-PAM compounds, are well known and have been usedfor many years as dispersants, both for dispersing oxygenated sludge inautomotive engines and mitigating fouling during crude oil processingoperations. The commercially available PIBSA-PAM compounds generallyhave a number average molecular weight (MN) within the range of fromabout 500 to about 2000, a nitrogen atom content within the range offrom about 1.0 to about 4.0 weight % and a total base number within therange of from about 40 to about 60 mg KOH per gram of PIBSA-PAMcompound. In the past, these commercially used PIBSA-PAM compounds havebeen made by reacting a conventional PIB with maleic anhydride or thelike using a chlorine facilitated process to produce a polyisobutylenesuccinyl anhydride (PIBSA). That is to say, the known PIBSA-PAMcompounds are generally produced by first reacting a conventional PIBwith maleic anhydride at elevated temperatures in the presence ofchlorine gas. The PIBSA so produced is then condensed with a polyamine(PAM) having a plurality of polar nitrogen atoms.

The production of PIBSA using conventional PIB takes place as follows:

Conventional PIB products are generally produced using an AlCl₃catalyst, and about 65% of the molecules of the polymeric product havedouble bonds that are 1,2,2-trisubstituted. The remainder of themolecules of the polymeric product have double bonds that are highlysubstituted, internal, and relatively non-reactive. The1,2,2-trisubstituted double bonds are somewhat reactive in a thermal,chlorine facilitated reaction with maleic anhydride, whereas the highlysubstituted internal double bonds are essentially non-reactive withmaleic anhydride. The PIBSA products are generally of low quality withhigh color and considerable char. Active PIBSA yields are generally lessthan 70%. Moreover, when reacting conventional PIB with maleic anhydrideusing a conventional “ene” reaction mechanism, it is possible to attachonly one maleic anhydride group to each PIB molecule. This limits thenumber of polar nitrogen atoms that can be incorporated into eachmolecule of a conventional PIBSA-PAM dispersant. As a consequence ofthese things, the efficiency of the conventional dispersants forpurposes of inhibiting and/or mitigating fouling is limited. Methodologyfor producing PIBSA-PAM products where the PIBSA is prepared by reactingconventional PIB with maleic anhydride in the presence of chlorine isdescribed in U.S. reissue patent no. Re. 26,330 (the “'330 reissuepatent”).

More recently, processes have been developed for producing what hasbecome known as highly reactive polyisobutylene (HR-PIB). In HR-PIB, apredominant portion of the molecules of the polymeric product havedouble bonds which are in a vinylidene terminal (alpha) position.Generally speaking, in commercial grades of HR-PIB, about 83 to 85% ofthe double bonds are in a vinylidene position. These vinylidene doublebonds react readily with maleic anhydride under thermal reactionconditions to produce PIBSA products, and in general, PIBSA yields are10 to 15% greater than when conventional PIB is utilized. Methodologyfor preparing PIBSA using HR-PIB as a reactant is described in Europeanpatent application no. 0 355 895 (EP '895), which also discusses the useof such PIBSA to make PIBSA-PAM. However, EP '895 does not discuss theuse of the PIBSA-PAM as a dispersant for inhibiting or mitigatingfouling of process equipment used for processing crude oils or the like.Moreover, the nitrogen content of the PIBSA-PAM described in EP '895 isquite low and in each case is far less than 2%.

SUMMARY OF THE INVENTION

A principal object of the invention is to provide an improved dispersantmaterial for inhibiting and/or mitigating crude oil fouling of processequipment. In particular it is an object of the invention to provide animproved dispersant having a chemical makeup which facilitates theincorporation therein of an increased number of polar sites capable ofchelating with undesirable carbonaceous materials contained in crudeoils and the like. Furthermore, it is an object of the invention toprovide an improved high quality PIBSA-PAM material which is producedfrom a clean, high quality PIBSA made using a PIB having a significantconcentration of vinylidene double bonds. In the sense of the invention,a clean PIBSA is one which is relatively clear, has a light color andcontains essentially no char or chlorine.

The problems inherent in the prior art are minimized, if not eliminatedcompletely, and the foregoing objects are achieved, as a result of thepresent invention which provides a PIBSA-PAM dispersant material formitigating crude oil fouling in chemical process equipment comprising areaction product of a polyamine and a polyisobutylene succinyl anhydridemade with a polyisobutylene having a vinylidene double bond content ofat least 50%. Desirably the reaction product has an active nitrogen atomcontent of at least about 2% by weight. In accordance with the conceptsand principles of the invention, the dispersant material mayadvantageously be prepared by thermally reacting the polyisobutylenewith maleic anhydride to produce polyisobutylene succinyl anhydride. Thepolyisobutylene succinyl anhydride may thereafter desirably be reactedwith a polyamine having 5 to 7 nitrogen atoms to produce PIBSA-PAM. Infurther accordance with the invention, the reaction product may have anMN which desirably ranges from about 400 to about 5000, and preferablyranges from about 500 to 2500. In further accordance with the invention,the active nitrogen atom content of the dispersant may desirably be inthe range of from about 2% to about 12% by weight, and mayadvantageously be at least about 3%, 4%, 5%, 6% or more, by weight. Instill further accordance with the invention, the PIBSA-PAM reactionproduct may beneficially be prepared by reacting the polyisobutylenesuccinyl anhydride with a polyamine at a molar ratio of polyisobutylenesuccinyl anhydride to polyamine desirably within the range of from about1:1 to about 5:1 and preferably within the range of from about 2:1 toabout 2.5:1. Ideally, the dispersant material of the invention mayinclude one or more of a second dispersant material, an antioxidant, anantipolymerant, a metal chelating chemical, a hydrocarbon solvent and anoxygen, nitrogen, sulfur or chlorine containing solvent.

In accordance with another desirable aspect of the invention, the sameprovides a crude oil composition wherein fouling has been mitigatedcomprising crude oil and an anti-fouling amount of the improveddispersant material described above dispersed in the crude oil. Infurther accordance with this aspect of the invention, the crude oilcomposition may desirably include from about 1 ppm to about 500 ppm (wt)of said dispersant material, may preferably include from about 5 ppm toabout 200 ppm (wt) of said dispersant material and ideally may includefrom about 10 ppm to about 150 ppm (wt) of said dispersant material.

In another important aspect, the invention provides a method formitigating crude oil fouling of chemical process equipment whichincludes providing a dispersant material comprising a reaction productof a polyamine and a polyisobutylene succinyl anhydride made with apolyisobutylene having a vinylidene double bond content of at least 50%,said reaction product having an active nitrogen atom content of at leastabout 2% by weight; and dispersing the dispersant material in a crudeoil wherein fouling properties are to be mitigated.

In another important aspect, the invention provides a dispersantmaterial for mitigating crude oil fouling in process equipmentcomprising a reaction product of a polyamine and a polyisobutylenesuccinyl anhydride, wherein the polyisobutylene succinyl anhydride ismade by a thermal process, and the reaction product has an activenitrogen content of at least about 2% by weight. Preferably, in accordwith this aspect of the invention, the polyamine has from 5 to 7nitrogen atoms. The dispersant of this aspect of the inventionpreferably has an active nitrogen atom content of at least about 5% byweight and ideally has an active nitrogen atom content of at least about6% by weight.

In accordance with yet another aspect of the invention, a crude oilcomposition is provided wherein the fouling characteristics thereof aremitigated. In accordance with this aspect of the invention, thecomposition comprises crude oil and an anti-fouling amount of animproved dispersant material as described above dispersed in the crudeoil. In further accord with this aspect of the invention, the crude oilcomposition preferably comprises from about 1 ppm to about 200 ppm (wt)of the dispersant material, desirably comprises from about 5 ppm toabout 100 ppm (wt) of the dispersant material and ideally comprises fromabout 10 ppm to about 25 ppm (wt) of the dispersant material.

In yet another important aspect, the invention provides a method formitigating crude oil fouling comprising providing a dispersant materialcomprising a reaction product of a polyisobutylene succinyl anhydrideand a polyamine, said polyisobutylene succinyl anhydride characterizedby having been made by a thermal process, said reaction product havingan active nitrogen atom content of at least about 2% by weight,desirably greater than about 4.8% by weight, preferably at least about5% by weight, and ideally at least about 6% by weight; and dispersingsaid dispersant material in a crude oil wherein fouling is to bemitigated.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

As mentioned above, the present invention provides an improveddispersant material for mitigating crude oil fouling of processequipment. In particular the invention provides an improved dispersanthaving a chemical makeup which facilitates the incorporation therein ofan increased number of polar sites capable of chelation with undesirablecarbonaceous materials such as asphaltenes contained in crude oils andthe like. Furthermore, the invention provides an improved high qualityPIBSA-PAM antifoulant dispersant material which is produced from aclean, high quality PIBSA produced from a PIB having a significantconcentration of vinylidene double bonds. In the sense of the invention,a clean PIBSA is one which is relatively clear, has a light color, andcontains essentially no char or chlorine.

Valuable PIB compositions having significant concentrations ofvinylidene double bonds that are highly useful in connection with thepresent invention are fully described in U.S. Pat. No. 6,562,913 (the“'913 patent”). Other valuable PIB compositions having utility inconnection with the present invention are fully described in UnitedStates patent publication no. U.S. 2002/0197497 A1 (the “'497 patentpublication”). The entireties of the disclosures of the '913 patent andthe '497 patent publication are hereby incorporated into the disclosureof the present application by this specific reference thereto. The '895European patent application mentioned above also describes PIBcompositions having significant concentrations of vinylidene doublebonds that are useful in connection with the present invention.

In accordance with the concepts and principles of the present invention,the methodology used for preparing the PIB compositions useful inconnection with the present invention is not critical. The only criticalfeature of the PIB compositions is that the same should includesignificant concentrations of polymeric molecules having vinylidenedouble bonds. Preferably, the molar concentration of molecules of havingvinylidene double bonds in the overall PIB composition should be atleast 50%, and desirably and ideally, this concentration may be 60%,70%, 80%, 90% or even greater, without deviating from the overallpurposes and objects of the invention. Moreover, the PIB compositionsuseful in accordance with the invention should preferably have an MN inthe range of from about 350 to about 5000, more preferably in the rangeof from about 600 to about 4000, desirably in the range of from about700 to about 3000, even more desirably in the range of from about 800 toabout 2000, and ideally in the range of from about 900 to about 1050. Ina highly preferred form of the invention, the PIB composition may havean M_(N) of about 950.

Generally, and in further accordance with the concepts and principles ofthe invention, the PIB compositions described above may desirably bereacted with maleic anhydride to form PIBSA products. The production ofPIBSA using HR-PIB and a 1:1 molar ratio or slight excess of maleicanhydride takes place according to the following reaction scheme:

Desirably the PIBSA forming reaction follows a “thermal” route such asis described in EP '895, where the PIB and the maleic anhydride aresimply mixed and heated together. Such a process minimizes theopportunity for chlorine residues to be present in the PIBSA. When PIBproducts that include significant concentrations of polymeric moleculeshaving vinylidene double bonds are reacted with maleic anhydride using a“thermal” route, the maleic anhydride is used very efficiently,resulting in products of high quality which are clear, have a lightcolor and contain essentially no char. Overall PIBSA yields are 10 to15% greater than when conventional PIB is utilized.

When PIB products which include significant concentrations of polymericmolecules having vinylidene double bonds are reacted with a substantialexcess of maleic anhydride (molar ratio of maleic anhydride to PIB ofsay 1.5:1 or greater), the PIBSA may be caused to include a significantconcentration of a di-maleated product. That is to say, more than onemolecule of maleic anhydride can be incorporated into the PIBSA productfor each molecule of PIB. This facilitates the incorporation of agreater amount of polyamine into the product, whereby to increase theoverall nitrogen content of the PIBSA-PAM product when the di-maleatedPIBSA is reacted with a polyamine. The di-maleated PIBSA product isbelieved to have the following molecular configuration:

With reference to the foregoing, it has been noted in accordance withthe present invention that the ability of a dispersant material tomitigate and/or inhibit crude oil fouling of process equipment may beenhanced by incorporating therein a larger number of polar sites capableof chelating with the undesirable carbonaceous materials contained incrude oils and the like. Needless to say, di-maleated PIBSA productshave twice as many locations as conventional PIBSA where the same arereactive with polar nitrogen containing polyamines. Accordingly, thecapacity of the PIBSA for taking on polar sites by reaction withpolyamines is substantially enhanced. However, it is to be understoodthat in accordance with the broad aspects of the invention, it is notnecessary for the PIBSA product to be di-maleated in order to achievethe benefits of the invention. Accordingly, the molar ratio of polyamineto PIB in the PIBSA of the invention may desirably range from 0.5:1 orless to as much as a theoretical value of 2:1 if the PIBSA is made froma PIB wherein 100% of the double bonds are vinylidene and each PIBmolecule is di-maleated. More conveniently, the molar ratio of polyamineto PIB in the PIBSA of the invention should be in the range of fromabout 1:1 to about 1.5:1. With further reference to the foregoing, andin further accordance with the invention, the average number of maleicanhydride groups per molecule of PIB in the PIBSA should desirably rangefrom about 0.5:1 to about 2:1. And ideally should range from about 1:1to about 1.5:1.

In further accordance with the concepts and principles of the invention,the PIBSA materials discussed above are reacted with polyamines to formPIBSA-PAM substances. A great number of potentially suitable polyaminecompounds are discussed in the '330 reissue patent identified above;however, the preferred amines for purposes of the present invention arethe ethylene amines such as triethylenetetramine, tetraethylenepentamineand pentaethylenehexamine. A particularly valuable ethylene aminematerial for use in accordance with the invention is a commerciallyavailable product of Dow Chemical Company which is known as HeavyPolyamine X (HPA-X). HPA-X is a complex mixture of linear, branched, andcyclic ethyleneamines, the principal components of which includetriethylenetetramine (<2.0 wt %), tetraethylenepentamine (2-25 wt %),pentaethylenehexamine (15-55 wt %) and higher molecular weightethyleneamines (30-75 wt %). On the average, each molecule of HPA-X has6.64 nitrogen atoms, and the same has a molecular weight ofapproximately 275 g/mole. Accordingly, the nitrogen content of HPA-X isabout 33.8 wt %. Here also, the exact ratio of PIBSA to PAM is notcritical, and the same, when expressed in terms of the molar ratio ofthe PAM to the maleic anhydride moieties of the PIBSA, may desirablyrange from about 0.5:1 to about 1:1.

It should further be noted in connection with the invention describedand discussed above, that sometimes fouling resulting from crude oilprocessing may be caused by more than one mechanism. In such cases, itis sometimes convenient and efficient to use a combination of dispersantchemicals. That is to say, the improved PIBSA-PAM of the invention maysometimes desirably be combined with other chemical additives to providea multi-functional additive to perform dispersing as well as otherfunctions. Chemicals which might be used with the improved PIBSA-PAM ofthe invention include, without limitation, anti-oxidants such astertiary butyl phenol, alkyl diphenyl amine, phenyl naphthyl amine anddioctyl diphenyl amine, antipolymerants such as di-tertiary-butylcresol, tris-nonyl phenol phosphite, amino nonyl phosphite, nitroxideand di-phenyl phosphite, and metal deactivators such asdisalicylidene-1,2-propane diamine.

EXAMPLE I

A preferred embodiment of an improved, high quality PIBSA-PAM materialproduced from a clean, high quality PIBSA made using a PIB having asignificant concentration of vinylidene double bonds is prepared in thefollowing manner:

-   -   1. 433 g of an HR-PIB product having an M_(N) of 950 and an        alpha vinylidene content of 83.6% is charged into glass reactor        and the reactor is heated to 300° F. for 1 hour while a vacuum        and N₂ sweep are applied thereto.    -   2. 67.04 g of Maleic Anhydride at 300° F. is added to the HR-PIB        in the reactor and the reaction mixture is heated to 450° F.    -   3. The reaction mixture is maintained at a reaction temperature        of 450° F. for 4.5 hours and thereafter a vacuum and N₂ sweep        are applied to the reactor for 1 hour to strip away any        unreacted Maleic Anhydride.    -   4. The product is a Polyisobutylene Succinic Anhydride (PIBSA).    -   5. 309.3 g of the PIBSA thus prepared is transferred to another        glass reactor and heated to 250° F.    -   6. 109.3 g of Heavy Polyamine X at 240° F. is added over a        period of 1 hour to the reactor containing the PIBSA while the        reaction temperature is maintained between 240° F. and 270° F.    -   7. The reaction temperature is then increased to 280° F. and        held at that level for 1 hour and 20 minutes.    -   8. The reaction temperature is then increased to 305° F. and        held at that level for 3 hours and 20 minutes.    -   9. A vacuum and N₂ sweep are applied to the reactor for 1 hour        to strip the polyisobutylene succinimide (PIBSA-PAM) product of        residual reactants, etc.    -   10. The final product is analyzed and determined to have a        nitrogen content of 8.9 weight percent %.

A commercially available PIBSA-PAM product made from conventional PIBand having a M_(N) of about 1300 was acquired for comparison purposes.This material and the improved PIBSA-PAM prepared in accordance withExample I were subjected to identical testing to determine the abilityof each material to inhibit and/or mitigate fouling in a chemicalprocess type environment. A Thermal Fouling Test Method (TFTM) was usedfor this purpose. The TFTM is an accelerated test method that isdesigned to reproduce the fouling problems experienced in refineryprocesses or petrochemical plants. The test temperatures are generallyhigher than those actually encountered in a commercial operation so thatsimilar problems may be reproduced in a shorter, more reasonable periodof time. The TFTM is not an exact simulation of refinery heat exchangerfouling, but by accelerating fouling through high fluid temperature, itprovides a valuable tool that yields results in a reasonable time. TheTFTM has been shown to correlate well with plant results and is,therefore, useful for research, investigating fouling, and developingantifoulants. The test is described in the literature. Wachel, L. J.,“Exchanger Simulator: Guide to Less Fouling,” Hydrocarbon Processing,November 1986, pp. 107-110.

In summary, the TFTM involves the use of a thermal fouling tester (TFT)which measures crude oil fouling. In the TFT, a crude oil sample iscirculated through a miniature heat exchanger with a carbon steel heatertube. The entire TFT system is pressurized to prevent vaporization ofthe sample at the high temperatures in the exchanger. Fouling isdetermined by measuring the fluid outlet temperature which varies as afunction of deposit formation on the heater metal surface. A greatertemperature degradation indicates a higher degree of fouling.

The TFTM is an excellent method for simulating the fouling which mightoccur in processing equipment as a result of the processing of crudeoils and the like and for measuring the efficiency of antifoulantmaterials. The effect of antifoulant materials for crude oil treatmentis described below.

EXAMPLE II Thermal Fouling Testing of Untreated Crude Oil

The thermal fouling characteristics of untreated crude oil is determinedusing the TFTM described above. The thermal fouling test results showthat the crude oil used in connection with these tests is a relativelyhigh fouling crude oil. Test conditions and test fouling results arepresented below. Exchanger heater metal temperature 700° F. Liquidoutlet temperature 510° F. Unit operating pressure 800 psig Exchangerheater metal type C/S 1018 Oil flow 3.0 cc/min Test time 180 minutesMeasured fouling  70° F.

EXAMPLE III Thermal Fouling Testing of Crude Oil Containing ConventionalPIBSA-PAM Antifouling Agent

A crude oil identical to the crude oil tested in Example I was blendedwith 100 ppm (wt) of the acquired PIBSA-PAM that was made withconventional PIB. This conventional commercially available PIBSA-PAM hadthe following characteristics: Average molecular weight (M_(N)) 1300Carbon content 82.87 wt % Hydrogen content 12.89 wt % Oxygen content 0.90 wt % Nitrogen content  4.8 wt % Carbon/Hydrogen atomic ratio  0.53 Total base number 114 mg/gm

The TFTM was used to determine the thermal fouling of the treated crudeoil using exactly the same operating conditions as used in Example II.Test results show that the crude oil treated with conventional PIBSA-PAMhas reduced fouling characteristics as compared with the untreated crudeoil. Test operating conditions and results are presented below.Exchanger heater metal temperature 700° F. Liquid outlet temperature514° F. Unit operating pressure 800 psig Exchanger heater metal type C/S1018 Oil flow 3.0 cc/min Test time 180 minutes Measured fouling  46° F.

EXAMPLE IV Thermal Fouling Testing of Crude Oil Containing a PIBSA-PAMAntifouling Agent Prepared from Improved PIBSA-PAM

A crude oil identical to the crude oil tested in Example I was blendedwith 100 ppm (wt) of the PIBSA-PAM made in accordance with Example I.This improved PIBSA-PAM had the following characteristics: Averagemolecular weight (M_(N)) 1300 Nitrogen content 8.9 wt % Total basenumber 132 mg/gm

The TFTM was used to determine the thermal fouling of the treated crudeoil using exactly the same operating conditions as used in Examples IIand III. The test results set forth below show that the crude oiltreated with the PIBSA-PAM of the invention that is made from a PIBhaving a significant content of vinylidene double bonds, has reducedfouling characteristics as compared with either the untreated crude oilor the crude oil treated with conventional PIBSA-PAM. Test operatingconditions and results are presented below. Exchanger heater metaltemperature 700° F. Liquid outlet temperature 507° F. Unit operatingpressure 800 psig Exchanger heater metal type C/S 1018 Oil flow 3.0cc/min Test time 180 minutes Measured fouling  30° F.

1. A dispersant material for mitigating crude oil fouling comprising a reaction product of a polyamine and a polyisobutylene succinyl anhydride made with a polyisobutylene having a vinylidene double bond content of at least 50%, said reaction product having an active nitrogen atom content of at least about 2% by weight.
 2. A dispersant material as set forth in claim 1, wherein said reaction product is prepared by thermally reacting said polyisobutylene with maleic anhydride to produce said polyisobutylene succinyl anhydride and thereafter reacting the polyisobutylene succinyl anhydride with a polyamine having 5 to 7 active nitrogen atoms.
 3. A dispersant material as set forth in claim 1, wherein said reaction product has a number average molecular weight which ranges from about 400 to about
 5000. 4. A dispersant material as set forth in claim 3, wherein said reaction product has a number average molecular weight which ranges from about 500 to
 2500. 5. A dispersant material as set forth in claim 1, wherein the active nitrogen atom content thereof is at least about 4% by weight.
 6. A dispersant material as set forth in claim 1, wherein the active nitrogen atom content thereof is at least about 6% by weight.
 7. A dispersant material as set forth in claim 2, wherein said reaction product is prepared by reacting said polyisobutylene succinyl anhydride with a polyamine at a molar ratio within the range of from about 0.5:1 to about 5:1.
 8. A dispersant material as set forth in claim 1, further comprising one or more of a second dispersant material, an antioxidant, an antipolymerant, a metal chelating chemical, a hydrocarbon solvent and an oxygen, nitrogen, sulfur or chlorine containing solvent.
 9. A crude oil composition wherein fouling has been mitigated comprising crude oil and an anti-fouling amount of a dispersant material as set forth in claim 1 dispersed in said crude oil.
 10. A crude oil composition as set forth in claim 9, comprising from about 1 ppm to about 500 ppm of said dispersant material.
 11. A crude oil composition as set forth in claim 9, comprising from about 5 ppm to about 200 ppm of said dispersant material.
 12. A crude oil composition as set forth in claim 9, comprising from about 10 ppm to about 150 ppm of said dispersant material.
 13. A method for mitigating crude oil fouling comprising: providing a dispersant material comprising a reaction product of a polyamine and a polyisobutylene succinyl anhydride made with a polyisobutylene having a vinylidene double bond content of at least 50%, said reaction product having an active nitrogen atom content of at least about 2% by weight; dispersing said dispersant material in crude oil wherein fouling is to be mitigated; and subjecting said crude oil to processing in an environment conducive to the occurrence of fouling.
 14. A method as set forth claim 13, wherein said reaction product is prepared by thermally reacting said polyisobutylene with maleic anhydride to present said polyisobutylene succinyl anhydride, and thereafter reacting the polyisobutylene succinyl anhydride with a polyamine having 5 to 7 nitrogen atoms.
 15. A method as set forth in claim 13, wherein said reaction product has a number average molecular weight which ranges from about 400 to about
 5000. 16. A method as set forth in claim 15, wherein said reaction product has a number average molecular weight which ranges from about 500 to
 2500. 17. A method as set forth in claim 13, wherein said dispersant material has an active nitrogen atom content of at least about 4% by weight.
 18. A method as set forth in claim 13, wherein said dispersant material has an active nitrogen atom content of at least about 6% by weight.
 19. A method as set forth in claim 14, wherein said reaction product is prepared by reacting said polyisobutylene succinyl anhydride with a polyamine at a molar ratio within the range of from about 0.5:1 to about 5:1.
 20. A dispersant material for mitigating crude oil fouling comprising a reaction product of a polyisobutylene succinyl anhydride and a polyamine, wherein said polyisobutylene succinyl anhydride is characterized by having been prepared by thermally reacting a polyisobutylene with maleic anhydride, said reaction product having an active nitrogen content of at least about 2% by weight.
 21. A dispersant material as set forth in claim 20, wherein said polyamine has from 5 to 7 nitrogen atoms.
 22. A dispersant material as set forth in claim 20, wherein said reaction product has a number average molecular weight which ranges from about 400 to about
 5000. 23. A dispersant material as set forth in claim 22, wherein said reaction product has a number average molecular weight which ranges from about 500 to
 2500. 24. A dispersant material as set forth in claim 20, wherein the active nitrogen atom content thereof is at least about 5% by weight.
 25. A dispersant material as set forth in claim 20, wherein the active nitrogen atom content thereof is at least about 6% by weight.
 26. A dispersant material as set forth in claim 21, wherein said reaction product is prepared by reacting said polyisobutylene succinyl anhydride with a polyamine at a molar ratio within the range of from about 0.5:1 to about 5:1.
 27. A dispersant material as set forth in claim 20, further comprising one or more of second dispersant material, an antioxidant, an antipolymerant, a metal chelating chemical, a hydrocarbon solvent and an oxygen, nitrogen, sulfur or chlorine containing solvent.
 28. A crude oil composition wherein the tendency for fouling has been mitigated comprising crude oil and an antifouling amount of a dispersant material as set forth in claim 20 dispersed in said crude oil.
 29. A crude oil composition as set forth in claim 28, comprising from about 1 ppm to about 500 ppm of said dispersant material.
 30. A crude oil composition as set forth in claim 28, comprising from about 5 ppm to about 200 ppm of said dispersant material.
 31. A crude oil composition as set forth in claim 28, comprising from about 10 ppm to about 150 ppm of said dispersant material.
 32. A method for mitigating crude oil fouling comprising: providing a dispersant material comprising a reaction product of a polyamine and a polyisobutylene succinyl anhydride made with a polyisobutylene having a vinylidene double bond content of at least 50%, said reaction product having an active nitrogen atom content of at least about 2% by weight; and dispersing said dispersant material in a crude oil wherein fouling is to be mitigated.
 33. A method for mitigating crude oil fouling as set forth in claim 32, wherein said polyisobutylene succinyl anhydride is characterized by having been made by a thermal process.
 34. A dispersant material as set forth in claim 1, wherein said reaction product is prepared by thermally reacting said polyisobutylene with maleic anhydride to present said polyisobutylene succinyl anhydride.
 35. A dispersant material as set forth in claim 20, wherein the active nitrogen atom content thereof is at least about 3% by weight.
 36. A dispersant material as set forth in claim 20, wherein the active nitrogen atom content thereof is at least about 4% by weight.
 37. A dispersant material as set forth in claim 1, wherein the active nitrogen atom content thereof is at least about 3% by weight.
 38. A dispersant material as set forth in claim 1, wherein the active nitrogen atom content thereof is at least about 5% by weight.
 39. A dispersant material as set forth in claim 1, wherein said polyisobutylene succinyl anhydride is made with a polyisobutylene having a vinylidene double bond content of at least 60%.
 40. A dispersant material as set forth in claim 1, wherein said polyisobutylene succinyl anhydride is made with a polyisobutylene having a vinylidene double bond content of at least 70%.
 41. A dispersant material as set forth in claim 1, wherein said polyisobutylene succinyl anhydride is made with a polyisobutylene having a vinylidene double bond content of at least 80%.
 42. A dispersant material as set forth in claim 1, wherein said polyisobutylene succinyl anhydride is made with a polyisobutylene having a vinylidene double bond content of at least 90%.
 43. A dispersant material as set forth in claim 1, wherein said polyisobutylene succinyl anhydride is made with a polyisobutylene having a vinylidene double bond content that is greater than 90%.
 44. A method for mitigating crude oil fouling as set forth in claim 32, wherein said reaction product has an active nitrogen atom content greater than 4.8% by weight. 